Recovery of mixed acids from mixed salts

ABSTRACT

A process for recovering concentrated mixed acids comprising HF from mixed salts at a high efficiency is disclosed. The process comprises the steps of providing an electrodialytic water splitter comprising at least one unit cell, each cell comprising a first compartment and a second compartment, feeding an aqueous solution comprising at least two salts formed from at least two different anions to the first compartment, one of said anions being fluoride, feeding a liquid comprising water to the second compartment, passing current through said electrodialytic water splitter to produce an aqueous product comprising mixed acids formed from the different anions in the second compartment, and an aqueous salt-containing product comprising a reduced concentration of said anions in the first compartment, and recovering aqueous products from the second compartment. The process is particularly useful in the production of concentrated HNO 3  at unexpectedly high current efficiencies, and has particular utility in the area of regenerating stainless steel pickling acid mixtures comprising HF and HNO 3 .

This application is a continuation of application Ser. No. 729,848 filedMay 3, 1985, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to an electrodialytic process for recoveringmixed acids from mixed salts. More particularly, the invention isdirected to the recovery of mixed acids comprising HF and, for example,HNO₃ from spent process materials such as pickling liquors by a processwhich employs a three-compartment electrodialytic water splitter.

Pickling baths, for example, are employed to remove scale, oxides, andother impurities from metal surfaces such as stainless steel. Thesebaths comprise inorganic acids such as hydrochloric acid, sulfuric acid,phosphoric acid, nitric acid, and hydrofluoric acid, and commonly aremixtures thereof. Eventually, the acids in these baths are exhausted dueto the reactions of the acids with the oxides, scale, etc. Consequently,the pickling acids are converted to a spent solution comprisingacidified mixed salts. This spent solution must then be disposed of andthe acids lost must be replaced. The acids, particularly hydrofluoricand nitric, are costly to replace. Moreover, the toxicity of the spentmaterials, especially hydrofluoric acid, can create significantenvironmental damage if improperly disposed of, and the large volumes ofthe exhausted baths add a very substantial cost to pickling processesdue to the cost of disposing of these materials.

Processes for regenerating processing materials are known. For example,U.S. Pat. Nos. 3,477,815 and 3,485,581 disclose processes for removingSO₂ from combustion gases employing a scrubbing solution which can bethermally regenerated, and U.S. Pat. No. 3,475,112 discloses a processfor removing SO₂ from combustion gases using a scrubbing solution whichcan be electrolytically regenerated. Recently, electrodialytic methodshave been disclosed for regenerating process solutions. In U.S. Pat.Nos. 4,082,835 and 4,107,015, processes are disclosed for regeneratingscrubbing solutions used in stripping SO_(x) from flue gases by feedingthe spent solutions through an electrodialytic water splitter.

While concentrated acids can be produced by electrodialytic watersplitting methods, such production is limited by the current efficiencyof producing these acids. For example, the current efficiency ofproducing 5% HNO₃ is only about 0.6. Therefore, many processes employingelectrodialysis produce relatively dilute acid solutions to insure highcurrent efficiency. For example, in U.S. Pat. No. 4,504,373, a processis disclosed for regenerating a dilute sulfuric acid solution for use inthe processing of rayon.

BRIEF DESCRIPTION OF THE INVENTION

We have unexpectedly discovered a process for recovering concentratedmixed acids comprising HF from mixed salts at a high current efficiency.The process comprises the steps of:

(a) providing an electrodialytic water splitter comprising at least oneunit cell, each unit cell comprising a first compartment and a secondcompartment;

(b) feeding an aqueous solution comprising at least two salts formedfrom at least two different anions to the first compartment, one of saidanions being fluoride;

(c) feeding a liquid comprising water to the second compartment;

(d) passing current through said electrodialytic water splitter toproduce an aqueous product comprising mixed acids formed from thedifferent anions in the second compartment, and an aqueoussalt-containing product comprising a reduced concentration of saidanions in the first compartment; and

(e) recovering aqueous products from the second compartment.

Our process is particularly useful in the production of concentratedHNO₃ at unexpectedly high current efficiencies, and has particularutility in the area of regenerating stainless steel pickling acidmixtures comprising HF and HNO₃.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically illustrates a three-compartment electrodialyticwater splitter employed for carrying out the process of the presentinvention.

FIG. 2 schematically illustrates a preferred embodiment of applicants'process employing a three-compartment electrodialytic water splitter ofthe type illustrated in FIG. 1.

FIG. 3 graphically illustrates the decrease in efficiency ofelectrodialytic water splitting processes as one attempts to produceincreasing concentration of a strong acid.

FIG. 4 graphically illustrates the efficiency of the reaction in thesalt compartment of a three-compartment electrodialytic water splitterwhen operated in accordance with the process of the present invention.

FIG. 5 graphically illustrates the substantially increased efficiencyfor producing a 5% concentration of HNO₃ when operating athree-compartment electrodialytic water splitter in accordance with theprocess of the present invention.

DETAILED DESCRIPTION

The preferred apparatus employed in performing the basic process of thepresent invention is known in the art as a three-compartmentelectrodialytic water splitter. A three-compartment electrodialyticwater splitter comprises at least one unit cell, each unit cellcomprising cation, water-splitting, and anion membranes arranged inalternating fashion to define base, acid, and salt compartments. Atypical unit cell is schematically illustrated as unit cell 13 in FIG.1.

Employed in each unit cell are means for splitting water into hydrogenions and hydroxyl ions (water-splitting membrane). Most preferably, themeans for splitting water into hydrogen and hydroxyl ions is a bipolarmembrane. Examples of bipolar membranes which are particularly usefulinclude those described in U.S. Pat. No. 2,829,095 to Oda et al. (whichhas reference to water splitting generally), in U.S. Pat. No. 4,024,043(which describes a single film bipolar membrane), and in U.S. Pat. No.4,116,889 (which describes a cast bipolar membrane). However, any meanscapable of splitting water into hydrogen and hydroxyl ions may be used;for example, spaced apart anion and cation membranes having waterdisposed therebetween.

The cation membranes employed in the electrodialytic water splitter maybe moderately acidic (e.g., phosphonic group-containing) or stronglyacidic (e.g., sulfonic group-containing) cation permselective membraneshaving a low resistance at the pH at which they are employed.Particularly useful cation membranes are Dupont's Nafion® acidicfluorocarbon membranes, especially Nafion® 110, 901, and 324 cationmembranes.

The anion membranes used in the electrodialytic water splitter arestrongly, mildly, or weakly basic anion permselective membranes. Usablemembranes are, for example, commercially available from Ionics, Inc.,Watertown, Mass. (sold as Ionics 204-UZL-386 anion membrane), or fromAsahi Glass Co. (sold under the trade name Selemion® AMV or ASV anionpermselective membranes).

FIG. 1 schematically illustrates a typical design of a three-compartmentwater splitter 10 comprising two unit cells. As shown, the watersplitter comprises, in series, an anode (e.g., a platinum anode), ananolyte compartment, alternating base B, acid A, and salt Scompartments, a catholyte compartment, and a cathode 12 (e.g., aplatinum cathode). The unit cells 13 and 13' are defined by seriallyarranged membranes as follows: bipolar membrane 13b, anion permselectivemembrane 13c, and cation permselective membrane 13a', and bipolarmembrane 13b', anion permselective membrane 13c', and cationpermselective membrane 13a", respectively.

In accordance with the invention, the anolyte and catholyte compartmentswould contain a salt, base or acid solution (e.g., KOH in thearrangement illustrated in FIG. 1), the base B and acid A compartmentswould initially contain a liquid comprising water, and the saltscompartment would initially contain a mixed salt solution comprising afluoride salt MF and a salt MX of a different (second) anion (e.g., KFand KNO₃). Splitting of the mixed salts into acid and base commences byapplying a direct current through the water splitter 10 from the anode11 to the cathode 12.

In the acid compartment, hydrogen ions (H⁺) are added via the functionof the bipolar membrane 13b. Simultaneously, anions (designated F⁻ andX⁻ in the drawings) of the salts are transported across the anionmembrane 13c into the acid compartment. The reaction of the hydrogenions with the anions yields a mixed acid product comprising HF and HX.The use of the designation X⁻ (and from that MX or HX) refers not onlyto monovalent anions other than F⁻ but also to divalent anions, such assulfates, and trivalent anions, such as phosphates. Ordinarily, theefficiency of HX acid production in the acid compartment would belimited by the leakage of H⁺ ions back into the salt compartment.Applicants have unexpectedly discovered that, due to the presence offluoride ions in the salt compartment, the hydrogen ions are believed topreferentially react with the fluoride to produce a bifluroide anion,HF₂ ⁻ which, in turn, is transported back across the anion membrane 13cin preference to the fluoride anion, F⁻ , thus returning the losthydrogen ion to the acid compartment. Consequently, more hydrogen ionsare available to react with the anion X⁻, the result of which is themore efficient production of HX.

Cations in the salt compartment simultaneously pass through the cationmembrane 13a to the base B compartment. In the base B compartment, thecations, M⁺, react with the hydroxyl ions generated by the bipolarmembrane 13b to produce a basified solution. Consequently, the solutionremaining in the salt compartment is depleted in both salts.

As indicated in FIG. 1, cations migrate through cation membrane 13a fromthe anolyte compartment and similarly pass from the base compartmentthrough the cation membrane 13a'" to the catholyte compartment.Therefore, the anolyte and catholyte solutions are typicallycontinuously recirculated from the anolyte compartment to the catholytecompartment and back (or the reverse) to maintain a substantiallyconstant concentration of base (salt or acid) in each compartment.

It should be understood that the electrodialytic water splitter can beoperated in a batch mode, a continuous mode, or variations thereof. Itshould also be readily apparent that product solutions or portionsthereof (e.g., when using a feed and bleed apportionment operation) berecycled for further concentration. Moreover, it should be apparent thatmechanisms for serial feed through the compartments (e.g., B to B') maybe employed. These and other modifications, changes and alterations tothe design of the water splitter will not affect the scope of theinvention and will be obvious to thos or ordinary skill.

The water splitter is ordinarily supplied with a direct current rangingfrom about 30 amps/ft² (≈300 A/m²) to about 200 amps/ft² (≈2000 A/m²),preferably from about 80 A/ft² (≈800 A/m²) to about 120 A/ft² (≈1200A/m²) amps. The system normally operates at a temperature of betweenabout 10° C. and about 80° C. with a temperature range of between about30° C. and 55° C. being preferred.

A preferred embodiment of the present invention is schematicallyillustrated in FIG. 2. Spent process material comprising fluoride anionsand anions of another kind, for example spent pickling bath liquorcomprising acidified fluoride and nitrate salts, is removed from themanufacturing operation and supplied through line 1 to a precipitationchamber 2. To the precipitation chamber 2, is supplied a basifiedsolution (e.g., KOH, NaOH, NH₄ OH, or mixtures thereof, preferably analkali metal hydroxide, and most preferably KOH) through line 17 forcontact with the spent process material. In the event the spent processmaterial contains heavy metal ions (for example, Ni, Fe, Cr, Mn, etc.),the basified solution will react to form hydroxides thereof which willprecipitate out. The resulting product (for example a suspension) isthen fed through line 3 to a filtration unit (e.g., a plate and framefilter press). In filtration unit 4, the precipitate is filtered fromthe resulting product and may be washed with, for example, watersupplied from line 5 via line 6, and/or with an aqueous depleted saltsolution from line 6. The remaining solid is then withdrawn via line 7.

The aqueous filtrate of soluble mixed salts comprising a fluoride saltis then fed via line 8 to each salt compartment of the three-compartmentelectrodialytic water splitter 10. A liquid comprising water is fed tothe acid compartment via line 9, and a liquid comprising water such asaqueous depleted salt solution supplied via line 14a is fed to the basecompartment via line 15.

The operation of a three-compartment electrodialytic water splitter isas described with respect to FIG. 1, with mixed acid product beingwithdrawn via line 11, depleted salt being withdrawn via line 12, andbasified solution being withdrawn via line 16. The mixed acid productfrom line 11 can be directly recycled to the manufacturing process(e.g., to a pickling bath), stored for subsequent use or sale, orrecycled through the electrodialytic water splitter for furtherconcentration or some combination thereof. The depleted salt solutionfrom line 12 can be split into two streams via lines 14a and 14b. Aportion of the aqueous depleted salt can be recycled (via line 6)through the filtration unit 4 and back to the salt compartment whileanother portion can be supplied to the base compartment lines 14a and 15for basification. In addition, the depleted salt may be used to dilutethe process liquor or may be concentrated by, for example, reverseosmosis or electrodialysis to yield a relatively concentrated saltsolution (which may be reintroduced into the water splitter) and arelatively pure water stream (which may be used for washing theprecipitate or as make-up water in the electrodialysis process). Thebasified solution (either as a relatively pure base or as a basifiedsalt solution when depleted salt is supplied) is recycled from theelectrodialytic water splitter via line 16 and 17 to the precipitationunit 2.

The process of the present invention is capable of operating with anaqueous mixed salt-containing solution having varied concentration.Typically, the concentration of the mixed salts should be at least about0.4 molal, and preferably is at least about 1 molal. More importantly,however, the concentration of fluoride anion in the mixed salts shouldbe at least about 0.1M, preferably at least about 0.2M, and mostpreferably at least about 0.4M. Generally, the fluoride concentration isbetween 0.1M and about 3.0M, preferably between about 0.2M and 2.0M andmost preferably between about 0.4M and 1.0M.

The liquid supplied to the acid compartment comprises water and isgenerally selected from the group consisting of water, aqueous acidsolutions or dilute salt solutions. The liquid supplied to the basecompartment also comprises water and is generally selected from thegroup consisting of water, aqueous basic solutions, and depleted saltsolutions (e.g., from the salt compartment). Feedstreams to both theacid and base compartments can be supplied either by independent supplysystems, through a recycle of all or part of the liquid removed from aparticular compartment, or some combination thereof.

Typically, the process is capable of producing HF at a concentration ofup to about 15% by weight and the additional acid or acids at a total wt% of up to about 12% at unexpectedly high efficiencies. FIG. 3graphically illustrates the efficiency for the production of HNO₃ fromKNO₃ as a function of HNO₃ concentration in the acid compartment of athree-compartment electrodialytic water splitter. FIGS. 4 and 5graphically illustrate the unexpectedly improved efficiency for theproduction of nitric acid from nitrate when fluoride is also present inthe salt compartment. The graphs were generated from test data gatheredfrom using an electrodialytic water splitter having unit cellscomprising an Asahi ASV anion membranes, cast bipolar membranes of thetype disclosed in U.S. Pat. No. 4,116,889, and Dupont Nafion® 324 cationmembranes to produce 5% by weight nitric acid. As is clearly indicatedfrom FIG. 3, the efficiency of nitric acid production dropped steadilyfrom about 0.8 at 1% HNO₃ to about 0.6 at 5% HNO₃, with continuouslydecreasing efficiency at higher concentrations. In accord with ourinvention, FIG. 4 illustrates the highly efficient transfer of fluorideand nitrate ions from the salt compartment to the acid compartment andsimilarly, FIG. 5 illustrates the highly efficient production of mixedacids in the acid compartment, in particular concentrated nitric acid.As is clearly indicated from FIG. 5, the efficiency of producing 5% byweight nitric acid remains at about 0.8, with an efficiency of about 0.7for a 7% by weight acid solution (as compared to an efficiency of about0.5 for a 7% nitric acid solution in the absence of fluoride). Moreover,FIGS. 4 and 5 illustrate a principal mechanism of the process of theinvention; namely, the preferential transfer of nitrate ions as comparedto fluoride ions and the corresponding increased rate of production ofnitric acid as compared to the rate of production of hydrofluoric acid.

The following examples illustrate the practice of the present invention.These examples should not be construed in any way as limiting theinvention to anything less than that which is expressly disclosed orwhich would have been obvious to one of ordinary skill in this arttherefrom.

EXAMPLE 1

Spent processing liquor having the following chemical composition wassubjected to pretreatment steps prior to being subjected toelectrodialytic splitting in accordance with applicants' invention:

    ______________________________________                                        Ion             % Concentration                                               ______________________________________                                        F.sup.-         ≈5.5                                                  NO.sub.3 .sup.- ≈12.7                                                 Heavy Metals    ≈6.7                                                  ______________________________________                                    

The density of the liquor was about 1.25 g/mL, and the acidity of theliquor was approximately 6.0 meq⁻ OH/mL to pH 7.

Samples of the liquor were initially treated with 2M NH₃ and 2M KOH todetermine the effectiveness for precipitating the heavy metals from theliquor and the filtration rates. Four hundred ml of the process liquorwas treated with 1200 ml of 2.0M base (KOH or NH₃). In each instance,the filtrate was collected and the cake washed with 400 ml H₂ O. Thecake was vacuumed dry and the wash collected. Fluoride ions and nitrateion analysis indicated the following approximate balance:

                  TABLE 1                                                         ______________________________________                                                   Volume      Wt. F.sup.-                                                                            Wt. NO.sub.3 .sup.-                           Solution   (mL)        (g)      (g)                                           ______________________________________                                        Sample 1 (NH.sub.3 treated)                                                   Pickle liquor                                                                             400        26.9     63.4                                          Filtrate   1200        15.6     46.8                                          Wash        470         4.1     10.7                                          Cake       (62.7 g)     9.4      5.0                                          Sample 2 (KOH treated)                                                        Pickle liquor                                                                             400        26.9     63.4                                          Filtrate   1670        25.2     64.1                                          Wash       1670        25.2     64.1                                          Cake       (72.8 g)     2.3      2.0                                          ______________________________________                                    

The results of these pretreatment steps indicated that KOH was generallymore effective in precipitating heavy metal ions.

EXAMPLE 2

For each test reported hereinbelow a three unit cell, three-compartmentelectrodialytic water splitter was employed. The electrodialytic watersplitter was constructed principally with ASV anion membranes, Nafion®324 cation membranes, and Allied bipolar membranes made in accordancewith the procedure disclosed in U.S. Pat. No. 4,116,889. Exposedmembrane area for each membrane is about 17 cm². Tests were conducted inbatch fashion with solutions being recirculated through the respectivecompartments of the electrodialytic water splitter. In most cases,estimates of current efficiency were made by measuring concentration andvolume changes.

COMPARATIVE TEST 1

The electrodialytic water splitter described was operated under thefollowing conditions:

    ______________________________________                                                 Current =                                                                             1.90 A                                                                Δ E =                                                                           12.4 (v) min.                                                         T =     28-35° C.                                             ______________________________________                                    

The salt compartment was initially charged with 1M KNO₃. Water wasinitially supplied to the acid base compartments. During the test (7200second in duration), 431 ml of 1.001M HNO₃ was metered to the basecompartment to keep the pH≈7. Concentration of HNO₃ in the acid and saltcompartments were determined periodically, as well as the volumes incalibrated reservoirs. Relevant concentrations and volumes are reportedin Table 2 below:

                  TABLE 2                                                         ______________________________________                                        ACID             SALT                                                                         Volume                  Volume                                Time(s)                                                                              % HNO.sub.3                                                                            (mL)      Time(s)                                                                              % HNO.sub.3                                                                          (mL)                                  ______________________________________                                         150   1.44     295        200   .028   495                                   1750   2.98     300       1800   .168   482                                   3600   4.52     305       3640   .355   468                                   5300   5.71     309       5330   .515   455                                   7100   6.78     314       7120   .638   445                                   ______________________________________                                    

The calculated current efficiency and acid concentration as a functionof time were plotted to generate FIG. 3. Also, it is important to notethe increased acidification of the salt as the testing time increased.This is the result of H⁺ ions leaking into the salt compartment.

Test 2

In accordance with the basic concept of the present invention, mixedsalts of KF and KNO₃ were supplied to the three-compartmentelectrodialytic water splitter described above. The three-compartmentelectrodialytic water splitter was operated under the followingconditions:

    ______________________________________                                                 Current =                                                                             1.90 A                                                                Δ E =                                                                           13.6 (v) min                                                          T =     28-37° C.                                             ______________________________________                                    

In addition to analysis for acidity, the acid and salt were analyzed byion chromatography for F⁻ and NO₃ ⁻. Results are tabulated in Table 3below:

                  TABLE 3                                                         ______________________________________                                        Salt                                                                          Time(s)                                                                              Meq/g H.sup.+                                                                             % F     % NO.sub.3                                                                             Volume (mL)                               ______________________________________                                         70    .003        5.26    2.43     386                                       1715   .012        5.09    1.02     368                                       3560   .006        4.28    0.24     355                                       5560   .004        2.71    0.05     327                                       7250   .003        1.11    0.02     309                                       ______________________________________                                        Acid                                                                          Time(s)                                                                              Meq/g H.sup.+                                                                             % HF    % HNO.sub.3                                                                            Volume (mL)                               ______________________________________                                         50    0.91         .93    2.89     227                                       1715   1.27        1.14    4.57     236                                       3515   1.62        1.61    5.06     241                                       5530   1.99        2.33    5.14     250                                       7210   2.25        2.90    4.92     255                                       ______________________________________                                    

Using the experimental data from Table 3, the efficiency for salttransfer and hydrogen ion production was calculated and is graphicallyillustrated in FIGS. 4 and 5. From the data, it is clear that nitratewas transported in preference to fluoride ions. From the salt analysis,apparently HF₂ ⁻ is transported in preference to fluoride ion as thesalt does not become very acidic during the experiment, even at highnitric acid concentrations.

Test 3

A three-compartment electrodialytic water splitter of a constructiondescribed above was charged with the following solutions:

    ______________________________________                                        Base Compartment 480 mL   0.5M KOH                                            Acid Compartment 305 mL   1% HNO.sub.3                                        Salt Compartment 415 mL   Filtrate of Sample 1                                (1.30% F, 3.90% NO.sub.3 .sup.-)                                              ______________________________________                                    

The three-compartment electrodialytic water splitter was operated underthe following conditions:

    ______________________________________                                                 Current =                                                                             1.90 A                                                                Δ E =                                                                           15.9 (V) min                                                          T =     26-38° C.                                             ______________________________________                                    

The process was operated in a batch mode. At the end of a batch, aportion of the acid was removed and replaced with H₂ O, and the salt wasremoved and replaced with fresh filtrate. The results of a three-batchtest are summarized in Table 4 below:

                  TABLE 4                                                         ______________________________________                                              Acid                          Current                                   Batch (meq/g)    Base N             Efficiency                                No.   Initial Final  Initial                                                                             Final                                                                              Duration(s)                                                                           Acid Base                             ______________________________________                                        1     0.16    1.32   0.54  1.25 8200    0.81 0.83                             2     0.91    2.00   1.25  1.85 9660    0.78 0.75                             3     1.47    1.99   1.85  2.17 5600    0.68 0.70                             ______________________________________                                    

The final acid from Batch No. 3 was 1.49% HF/8.52% HNO₃ at a currentefficiency of about 0.7.

Test 4

A three-compartment electrodialytic water splitter of generally the sameconstruction described above was charged with the following solutions:

    ______________________________________                                        Base Compartment 500 mL   0.4 N KOH                                           Acid Compartment 300 mL   1% HNO.sub.3                                        Salt Compartment 500 mL   Filtrate of Sample 2                                (0.80M KF, 0.6M KNO.sub.3)                                                    ______________________________________                                    

The three-compartment electrodialytic water splitter was operated underthe same conditions as in Test 3. The process was again operated in abatch mode, with the replacement of salt solution occurring at the endof Production Batch No. 1. The results of the two batch test arereported in Table 5 below:

                  TABLE 5                                                         ______________________________________                                              Acid                          Current                                   Batch (meq/g)    Base N             Efficiency                                No.   Initial Final  Initial                                                                             Final                                                                              Duration(s)                                                                           Acid Base                             ______________________________________                                        1     0.16    1.63   0.40  1.34 9500    0.89 0.90                             2     1.14    2.19   1.34  2.05 9000    0.76 0.84                             ______________________________________                                    

The salt was 0.41M KF/0.01 KNO₃ after Batch No. 1 and 0.53M KF/0.03MKNO₃ after Batch No. 2. The acid after Batch No. 1 was about 0.63MHF/1.07M HNO₃, and after Batch 2 was about 0.81M HF/1.53M HNO₃. Noteagain the high currency efficiency for each batch.

EXAMPLE 3

Four batches of KF/KNO₃ filtrate were prepared from a spent processliquor for use in a five-day test. The first two batches were preparedby KOH precipitation followed by a precipitation wash with 400 ml of H₂O. For batches 3 and 4, the precipitate was washed with 300 ml ofdepleted salt from previous batches and 300 ml of H₂ O. For Batches 3and 4, base generated by electrodialytic water splitting of Batches 1and 2 was used to prepare the salt feed with fresh KOH being added toadjust the concentration of the generated base to 2M and to make-up.After each batch run, the acid and base were drained to 500 ml. Thedrained acid was replaced with fresh water and the drained base wasreplaced with depleted salt from the previous batch. The electrodialyticwater splitter employed was of the same construction as theelectrodialytic water splitter used in Test 4 of Example 1. Theelectrode rinse flow in Batches 1 and 2 was K₂ SO₄ and in Batches 3 and4 was 0.5M KOH. The results of the batch runs are summarized in Table 6below:

                  TABLE 6                                                         ______________________________________                                                                            Approximate                                                                   Current                                   Batch No.                                                                             Duration Hr. Initial Final  Efficiency                                ______________________________________                                        Acid (meq/g)                                                                  1       23.0         0.16    1.67   .84                                       2       19.8*        0.33    1.54   --                                        3       23.7         0.36    1.76   .81                                       4       23.2         0.42    1.84   .82                                       Base (N)                                                                      1       23.0         0.5     1.97   .85                                       2       19.8*        0.39    1.24   --                                        3       23.7         0.34    1.30   .85                                       4       23.2         0.38    1.32   .82                                       Salt N                                                                        1       23.0         1.28    0.47   .92                                       2       19.8*        1.24    0.61   --                                        3       23.7         1.30    0.23   .87                                       4       23.2         1.32    0.41   .89                                       ______________________________________                                         .sup.* Current <1.9 A for undertermined time; electrode rinse flow            (through anolyte and catholyte compartments) was blocked by a precipitate     of K.sub.2 SO.sub.4                                                            2.9 hours at 1.30 A                                                     

A mathematical analysis of the solution from Batch No. 4 confirming theexperimental results is summarized below:

                                      TABLE 7                                     __________________________________________________________________________    Initial Salt (4.5 L) 0.48M NO.sub.3.sup. - ; 0.84M F.sup.-                                                 (Total by IEX ≈ 1.32M)                   Final Salt (3.76 L) .005M NO.sub.3.sup. - ; 0.39M F.sup.-                                                  (Total by IEX ≈ 0.4M)                    *IEX = Ion Exchange                                                           Δ NO.sub.3.sup. - = 4.5 L × .48 moles/L - 3.76 L × .005     moles/L =                    2.14 moles                                       Δ F.sup.-  = 4.5 L × .84 moles/L - 3.76 L × .39 moles/L     =                             2.31 moles                                      Total =                      4.45 moles lost                                  Theoretical yield =          4.93 moles lost                                  Current Efficiency (η) = 4.45/4.93 ≈ .90                          Initial Acid (2.50 L) 0.19M HNO.sub.3 ; 0.22M HF                                                           (Total H.sup.+ ≈ 0.42M)                  Final Acid (2.76 L) 0.94M HNO.sub.3 ; 0.97M HF                                                             (Total H.sup.+ ≈ 1.84M)                  Δ HNO.sub.3 = (.94) (2.76) - (.19) (2.50) =                                                          2.12 moles HNO.sub.3 gained                      Δ HF = (.97) (2.76) - (.22) (2.50) =                                                                  2.13 moles HF gained                            Total =                      4.25 moles                                       Theoretical yield =          4.93 moles gained                                Current efficiency (η)   ≈.86                                     __________________________________________________________________________

As is quite clear from the results of applicants' experiments, theprocess operates at current efficiencies which are unexpectedly higheras compared to the efficiency attainable for the production of a singlestrong acid.

The above description gives a detailed discussion of applicants basicinvention and of applicants preferred embodiments. It will be obvious tothose of ordinary skill in the art that various modifications andchanges and/or alterations may be made without varying the scope of thepresent invention as defined by the appended claims.

We claim:
 1. A process for recovering a mixed acid solution comprisinghydrofluoric acid from a solution comprising salts of the acids to berecovered comprising the steps of:(a) providing an electrodialytic watersplitter comprising at least two unit cells, each unit cell comprising ameans for splitting water comprising a bipolar membrane or spaced apartanion and cation membranes, a first compartment and a secondcompartment, said electrodialytic water splitter additionally comprisinga single pair of anode and cathode electrodes said at least two unitcells being between the anode electrode and the cathode electrode; (b)feeding an aqueous solution comprising at least two salts formed from atleast two different anions to the first compartment, one of said anionsbeing fluoride anions; (c) feeding a liquid comprising water to thesecond compartment; (d) passing current through said electrodialyticwater splitter to produce an aqueous product comprising mixed acidsformed from the different anions in the second compartment, and anaqueous salt-containing product comprising a reduced concentration ofsaid anions in the first compartment; and (e) recovering aqueous productcomprising hydrofluoric acid from the second compartment.
 2. The processof claim 1 wherein the at least one unit cell further comprises a thirdcompartment.
 3. The process of claim 2 wherein a liquid comprising wateris fed to the third compartment, and wherein a basified aqueous solutionis produced in the third compartment upon passing the currenttherethrough.
 4. The process of claim 3 further comprising the step ofpretreating a spent process material comprising the at least twodifferent anions, one of which is fluoride anion, with the basifiedaqueous solution to produce the aqueous solution.
 5. The process ofclaim 4 wherein the spent process material is spent pickling liquor. 6.The process of claim 5 wherein the aqueous solution comprises alkalimetal fluoride and alkali metal nitrate.
 7. The process of claim 4wherein the spent process liquor is spent stainless steel picklingliquor.
 8. The process of claim 7 wherein the spent stainless steelpickling liquor further comprises nitrate ions.
 9. The process of claim8 wherein the basified aqueous solution comprises aqueous potassiumhydroxide.
 10. The process of claim 1 wherein another of said at leasttwo different anions is selected from the group consisting of chloride,sulfate, nitrate, and phosphate.
 11. The process of claim 1 furthercomprising the step of pretreating a spent process material comprisingthe at least two different anions, one of which is fluoride anion, toproduce the aqueous solution.
 12. The process of claim 11 wherein thestep of pretreating the spent process material comprises contacting thespent process material with a basified aqueous solution.
 13. The processof claim 1 wherein the means for water splitting is a bipolar membrane.14. A process for recovering mixed acids from spent stainless steelpickling liquor comprising at least two different anions, one of whichif fluoride anion, and heavy metal cations comprising the steps of:(a)contacting the spent stainless steel pickling liquor with a basifiedaqueous solution to produce a solution a solution comprising salts ofthe acids to be recovered, one of which is a fluoride salt, and aprecipitate comprising heavy metal ions; (b) recovering saidprecipitate; (c) subjecting the solution comprising salts toelectrodialytic water splitting in an electrodialytic water splitter toproduce a mixed acid product comprising hydrofluoric acid, theelectrodialytic water splitter comprising at least two unit cells, eachunit cell comprising a means for splitting water comprising a bipolarmembrane or spaced apart anion and cation membranes, a first compartmentand a second compartment, said electrodialytic water splitteradditionally comprising a single pair of anode and cathode electrodessaid at least two unit cells being between the anode electrode and thecathode electrode; and (d) recovering the mixed acid product from one ofthe compartments.
 15. The process of claim 14 wherein the means of watersplitting is a bipolar membrane.